JP2002524438A - Esters with musk aroma and their use in perfumery - Google Patents

Abstract

(57) [Summary] Formula (I): [Wherein the symbols R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom or a methyl group or an ethyl group, and the symbol X represents an oxygen atom or a formula (A): Wherein n is an integer of 1 to 3, and symbols R ⁶ and R ⁷ each represent a hydrogen atom or a methyl group or an ethyl group, and R ⁵ represents a C ₁ -C ₄ line. A branched or branched alkyl or alkoxy group, a C ₂ -C ₄ linear or branched alkenyl group or a formula: — (O) C—Y—R ⁸ (wherein Y represents the same as X, R ⁸ represents a C ₁ -C ₄ linear or branched alkyl group or a C ₂ -C ₄ linear or branched alkenyl group). Are novel compounds which give the products to which they are added a musk-smooth, voluminous and extremely sticky note.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the field of perfumery. More particularly, the present invention relates to esters derived from 1- (3,3-dimethyl-1-cyclohexyl) -1-ethanol having outstanding aroma properties.

[0002] Esters according to the invention as defined by the formula (I) below exhibit valuable useful odor properties and can therefore be used in the manufacture of perfumes, fragrance formulations and fragrance products There was found. The esters are used to give a musk-type aroma effect.

[0003] In the field of compounds having a musk aroma, over the past decade, some compounds widely used in the field of perfumery can be replaced, and their use has been increasing for toxicological and ecological reasons. There has been significant activity arising from the need to find new musk aroma compounds that are becoming increasingly restricted. The esters according to the invention are products which satisfy the requirements for perfuming compounds, which can replace the known compounds mentioned above.

The prior art, in particular DE-A 19 23 223, describes 1- (3
, 3-dimethyl-1-cyclohexyl) -ethanol are disclosed. However, no musk aroma from the disclosed compounds is described. The olfactory properties of this known compound are generally known as floral-woody (floor).
ral-woody) type.

On the other hand, US Pat. No. 5,166,412 discloses the following types of compounds:

[0006]

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Wherein R is a C ₁ -C ₂ alkyl group, wherein the compound has an amblet seeds type, ie, a smell of Williams peers. Recalling full-tay-peer (
It shows a musk-type aroma characterized by strong fruit-pear notes.

[0008] Surprisingly, compounds described by formula (I) as defined below are
It has been found that the compound of the formula (II) is completely different from the musk aroma and has a musk aroma which is extremely highly evaluated in the preparation of perfume.

[0009] Accordingly, an object of the present invention is to provide a novel compound which is useful as a perfume component to give a musk-type fragrance.

[0010] The purpose of this is to formula (I):

[0011]

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[Wherein the symbols R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom or a methyl group or an ethyl group, and the symbol X represents an oxygen atom or a formula:

[0013]

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(Wherein n is an integer of 1 to 3, symbols R ⁶ and R ⁷ represent a hydrogen atom or a methyl group or an ethyl group), and R ⁵ represents C _{1 to} C ₄ A linear or branched alkyl group or an alkoxy group of C ₂ -C _4, a linear or branched alkenyl group of the formula: — (O) C—Y—R ^{8 wherein} Y is the same as X , R ⁸ represents a C ₁ -C ₄ linear or branched alkyl group or a C ₂ -C ₄ linear or branched alkenyl group). You.

According to an advantageous embodiment of the invention, the general formula (III):

[0016]

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Wherein X is an oxygen atom or an unsubstituted methylene group or an ethylene group, and R ⁵ is a group as defined in Formula 1 having 1 to 3 carbon atoms. I do.

The esters of the above formulas (I) and (III) are new compounds.

Another object of the invention is to use the compounds of the above formula in the field of perfumes as well as perfumes, perfumes and perfumed products containing said compounds.

The compound of the present invention has a slight fruity ambrite therein.
FIG. 2 shows a musk aroma note in which an associative odor can be found, which is a compound of the prior art, ie of the formula (I)
Obviously less pronounced than in the compound according to I). The overall olfactory impression of the compounds of the present invention is generally that of a musk aroma compound with a sweet and heavy associative odor, which is closer to the so-called polycyclic musk but lighter and more sticky. This is quite different from the impression of the compound of formula (II), which shows a harsh olfactory note.

The compounds of the present invention may be present in the four stereoisomeric forms in pure form or as a mixture of stereoisomers. The present invention therefore includes all these possible compounds and all possible individual isomers. Since the olfactory notes of each of these isomers are different from the olfactory notes of the other isomers, the odor of all possible isomer mixtures will also differ from that of any given diastereomer or enantiomer. It can vary as a function of content.

Furthermore, among the advantageous compounds identified above according to the invention according to formula (III), the best olfactory characteristics are the alcohols used as starting products for the synthesis of some compounds according to the invention (+)-(1S, 1'R) -1- (3 ', 3'-dimethyl-1
It could also be established that it is represented in the isomer of the ester of the invention derived from '-cyclohexyl) -1-ethanol.

The most advantageous compounds of the present invention include, in particular, 1-[(3,3-dimethyl-1-
Cyclohexyl) ethoxycarbonyl] methylpropanoate. This compound is known as Galaxolide (registered trademark) (7,8-dihydro-4,6,6,7,8,8-hexamethyl-6H-cyclopenta [9]-
2-benzopyran; International Flavors a, USA
and the natural sweet musk odor with a classic musk-type fragrance reminiscent of the fragrance of N.Fragrances and a soft associative scent, giving an olfactory impression with sufficient volume . Also, the nuances of bright ambrettes with undernotes reminiscent of the scent of green flutes (
ambette nuance) is also known. The compounds of the invention are distinctly tenacious and heavier than the musk flavors of the known compounds when compared with the flavors of the compounds according to the prior art, which makes them particularly useful in base notes in the flavoring and perfuming formulations of the musk flavor. Generates musk aroma which makes it useful for creating.

The above-mentioned aroma characteristics are obtained by the isomer having the configuration of (1S, 1′R), that is, (1S, 1 ′).
R) -1-[(3 ', 3'-Dimethyl-1'-cyclohexyl) ethoxycarbonyl] methylpropanoate is best represented by this isomer which makes the compounds of the present invention special components of the present invention. .

In addition, mixtures which also contain large amounts of said isomers as well as their enantiomers or other stereoisomers give the scent effect evaluated. Thus, the most advantageous mixtures of the isomers according to the invention are also preferred embodiments of the invention.

The compounds according to the invention can be used in particular in all fields of modern perfumery. Here, mention is made of the use in fine perfumes, ie the use for the production of perfumes and colons from which the original olfactory effect is obtained.

The compounds can also be used as functional perfumes. Non-limiting examples of this type of application are soaps, bath and shower gels, shampoos, deodorants and antiperspirants, air fresheners.
and liquid and solid detergents and textile softeners for textile treatment.

In these applications, compounds (I) and (III) can be used alone or in mixtures with other flavoring ingredients, solvents or auxiliaries currently used in the field of perfumery. The nature and type of these common components need not be described in further detail here, nor are they exhaustive, but the person skilled in the art will depend on their general knowledge and on the correlation between the nature of the product to be perfumed and the desired olfactory effect. The common component could be selected as a function. These scented components are not only essential oils of natural or synthetic origin, but also various chemicals such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, heterocyclic compounds with sulfur and nitrogen. Belongs to species. In addition, many of these components can be found in reference textbooks (eg, the
book of S.C. Arctander, Perfume and Flav
or Chemicals, 1969, Montclair, New Jers
ey, USA, or more recent editions), or other works of the same type.

The proportions in which the compounds according to the invention can be incorporated in the various products mentioned above vary within a wide range of values. These values are based on the nature of the common components in a given formulation when the compounds of the present invention are used in a mixture with flavoring common components, solvents or adjuvants currently used in the art. It depends not only on the properties but also on the nature of the article or product that one wishes to perfume and the scented effect sought.

By way of example, mention may be made of a typical concentration of the order of 5 to 10% by weight of the compound, or even a concentration of 20% by weight, based on the weight of the scented formulation into which the compound is incorporated. it can. Concentrations much lower than the above are those of compound (I) or (III)
) Can be used when used directly for flavoring of the various consumer products mentioned above.

The compounds of the present invention are generally prepared by esterifying an alcohol of formula (IV) below with each acid of formula (V) or a suitable derivative thereof. This reaction is illustrated in the following Scheme I, where the symbols R ^{1 to} R ⁵ and X represent those shown in Formula (I).

Scheme I:

[0033]

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Suitable derivatives of acid (V) include, for example, acid halides such as chloride. Other suitable derivatives are well known to those skilled in the art. If it is desired to synthesize an optically active compound of the formula (I), the corresponding optically active alcohol of the formula (IV) is used in the esterification reaction. According to a preferred embodiment of the invention, 1- (3,3-dimethyl-) is used as starting alcohol for the preparation of the preferred compounds of the invention.
1-cyclohexyl) -1-ethanol or one of its enantiomers is used.

If the acids of the formula (V), in each case the appropriate derivatives thereof, are not obtained or do not react as desired, the following formula (VI) wherein H is an oxygen atom and the symbol R ¹
To R ⁴ represent an alcohol of the formula (I)], an acid of the formula (VII) wherein R ⁵ represents an acid of the formula (I) or a suitable derivative of each of these acids For example, in an esterification reaction with a halide.

Scheme II:

[0037]

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The alcohol of formula (VI) can be obtained by saponification of some compounds of the invention of formula (I) when X is an oxygen atom.

In the above process for preparing the compounds of the invention, the alcohols (IV) and (
The stereochemistry of VI) is retained. The stereochemistry of the compounds according to the invention is therefore that of the alcohol used as starting product.

Now, specific reaction conditions are described in the following Examples, in which abbreviations represent their ordinary technical meaning and temperatures are given in degrees Celsius (° C.); NMR spectral data (chemical shift δ ) Are given in ppm relative to TMS as internal standard. The invention is also illustrated by examples describing the use of the compounds of the invention in perfumery.

Embodiments of the Invention Example 1 Preparation of a Compound of Formula (I) a) (1S, 1′R) -1-[(3 ′, 3′-dimethyl-1′-cyclohexyl) ethoxycarbonyl] methylpropa Noate (1S, 1'R) -1- (3 ', 3'-dimethyl-1'-cyclohexyl)-
1-ethanol (HR Ansari, Tetrahedron 29, 15
59 (1973) by the method described by (+)-β-citronelene (F
luka), 3 g of [α] ^D ₂₀ = + 11.6 °, containing about 17% of other stereoisomers or purchased from DRT (France) and 1.52 g of pyridine were dissolved in 50 ml of diethyl ether. . Next, 2-chloro-2-oxoethylpropanoate dissolved in 20 ml of diethyl ether (FK Thayer,
Organic Synthesis Col. Vol. 1 (1932), p
. 2.9 g) were added for 10 minutes. The reaction mixture was then stirred for 30 minutes, after which another portion of 2-chloro-2-oxoethylpropanoate was added. After a reaction time of 1 hour, the reaction was quenched by addition of 5 ml of aqueous HCl (1M) and the mixture was extracted with ether. After flash column chromatography of the extract and concentration of the solution, the crude product thus obtained is separated by 120 ° / 9 × 10 ²
Distillation at Pa gave (1S, 1′R) -1-[(3 ′, 3′-dimethyl-1′-cyclohexyl) ethoxy-carbonyl] methylpropanoate. The yield was 4.12 g (79.5%).

[0042]

(Equation 1)

According to the production method described in a), (1R, 1 ′S) -1- (3 ′, 3′-dimethyl-
1-cyclohexyl) -1-ethanol [<< (-)-cyclademol (cycl)
ademol) >>; Source: DRT, France; [α] ^D ₂₀ = -10.4 °, containing about 18% of other stereoisomers], (1R, 1 ′S) −1 −
[(3 ', 3'-Dimethyl-1-cyclohexyl) ethoxycarbonyl] methylpropanoate was obtained. The analytical data (NMR, MS) of this was identical to that described under a).

B) (1S, 1′R) -1-[(3 ′, 3′-dimethyl-1′-cyclohexyl) ethoxycarbonyl] methylbutanoate The reaction is 2-chloro-2-oxoethylbutano Eat (produced according to the above literature)
Performed as above under a) with 4.78 g. Yield 120 ° / 6 × 1
5.22 g (95.8%) of product having an O ² Pa.

[0045]

(Equation 2)

C) (1S, 1′R) -1- (3 ′, 3′-dimethyl-1′-cyclohexyl)
Ethyl 4-oxohexanoate 4-oxo-hexanoic acid (GL Hommet et al., Synth
. 1.09 g (8.4 manufactured by Commun, 26, 3897 (1996)).
mmol) was converted to 1.25 g (8 mmol) of (1S, 1'R) -1- (3 ', 3'-dimethyl-1-cyclohexyl) -1-ethanol and 70 ml of toluene.
It was mixed with toluenesulfonic acid (0.012 g). The reaction mixture was heated under reflux for 15 hours on a Dean-Stark type separator. The resulting solution was washed with water, saturated NaHCO ₃ solution and again with water, after which the solvent was removed under reduced pressure. Bulb to bulb (bul
After distillation at 140 ° / 5 × 10 ² Pa in a b-to-bulb apparatus, the product 0
. 84 g (39%) were obtained.

[0047]

(Equation 3)

D) (1S, 1′R) -1- (3 ′, 3′-dimethyl-1-cyclohexyl) ethyl 5-oxohexanoate (1S, 1′R) -1- (20 ml in dichloromethane) 2.00 g (12.8 mmol) of 3 ', 3'-dimethyl-1-cyclohexyl) -1-ethanol, 5-
To a solution of 1.66 g (12.8 mmol) of oxo-hexanoic acid and 0.26 g of 4-dimethyl-aminopyridine was added 2.06 g (14%) of dicyclohexylcarbodiimide.
. (1 mmol). The solution is stirred for 90 minutes, filtered through Celite®, dried over MgSO ₄ and filtered. After evaporation of the solvent a yellow oil (3
. 0 g), which was distilled in a bulb-to-bulb apparatus at 160 ° / 1 × 10 ³ Pa to give 2.12 g (62%) of the desired product. .

[0049]

(Equation 4)

E) (1S, 1′R)-[1- (3 ′, 3′-dimethyl-1′-cyclohexyl) ethoxycarbonyl] methylmethyl oxalate i) (1S, 1′R) -1- ( 3 ', 3'-dimethyl-1'-cyclohexyl)
Ethyl hydroxyacetate This alcohol is (1S, 1'R)-[1- (3 ', 3'-dimethyl-1'-
Cyclohexyl) ethoxycarbonyl] methyl propanoate. For this purpose 50.0 g (185 mmol) of the same compound in 500 ml
Was dissolved in 250 ml of methanol in the flask. After cooling the mixture to −78 °, a solution containing about 5.4 M sodium methoxide in methanol (34.3 ml, 185 mmol) was added for 30 minutes, then stirring was continued at −50 ° for 90 minutes, The reaction mixture was then neutralized at this temperature with 100 ml of aqueous HCl (2M). The mixture was extracted with diethyl ether and neutralized by washing with a saturated NaHCO ₃ solution and then with water. After drying and concentration of the organic phase, the crude product is
(Vigreux) column to distill at 62 ° / 5 × 10 ² Pa to give the desired product 2
3.65 g (60%) were obtained.

[0051]

(Equation 5)

The compound was then esterified in ii) as described below.

Ii) 2 g (9.4 mmol) of the product obtained in i) are mixed with 25 ml of diethyl ether
Mixed with 1.1 g (14 mmol) of pyridine in
7 g (14 mmol) were added dropwise for 10 minutes and esterified. Temperature in ice bath 3
Maintained at 0 ° C., the mixture was stirred for 30 minutes and hydrolyzed with 3 ml of aqueous HCl (2M). The ether phase was washed with a saturated NaHCO ₃ solution and then with water. After drying and filtration, the solution is concentrated and added in a bulb-to-bulb apparatus.
Distillation at ° / 3 × 10 ² Pa gave 2.59 g (92%) of product.

[0054]

(Equation 6)

F) (1S, 1′R) -1-[(3 ′, 3′-dimethyl-1-cyclohexyl)
Ethoxycarbonyl] methyl 2-propenoate This compound was converted to alcohol (1S, 1′R) -1- (3 ′, 3′-dimethyl-1)
-Cyclohexyl) ethylhydroxyacetate (1) e) obtained as described under i))). 1 g (4.67 ml) of this alcohol was added over 10 minutes at 0 ° C. to a suspension prepared from 0.21 g (5.14 mmol) of a 60% suspension of NaH in mineral oil and 20 ml of THF. This suspension is added at room temperature for 30 minutes.
After stirring for 2 minutes and then cooling the mixture to -20 °, 0.47 g of acryloyl chloride
(5.14 mmol) was added. The mixture was warmed to room temperature and stirred at this temperature for 5 hours, after which another 0.47 g (5.14 mmol) of acryloyl chloride and 0.21 g of a 60% suspension of NaH in mineral oil were added. Stirring was continued for 2 hours, then the reaction was quenched with water and the solution was extracted with ether. Extract the organic extract with aqueous HCl (1M)
, Saturated NaHCO ₃ solution and water, and dried over MgSO ₄ . After evaporation of the solvent, the crude product is transferred in a bulb-to-bulb apparatus at 120 ° / 4.
Distillation at x10 ² Pa gave 1.13 g (90%) of the desired product.

[0056]

(Equation 7)

G) (1S, 1′R) -1-[(3 ′, 3′-dimethyl-1-cyclohexyl)
Ethoxycarbonyl] methyl 2-butenoate This compound was prepared as described above under f), except that acryloyl chloride was replaced by crotonoyl chloride (0.49 g, 4.67 mmol), which was added at room temperature. After drying and evaporating off the solvent, 1.43 g of an oil are obtained, which is chromatographed on silica and then in a bulb-to-bulb apparatus at 120 ° / 4.
x10 distilled at ² Pa to give the desired product 0.83g (71%).

[0058]

(Equation 8)

Example 2 Preparation of a scented formulation A base scented formulation was prepared from the following ingredients: Ingredients parts by weight amyl acetate 50 (E) -3-hexenyl acetate 10 γ-undecalactone 300 ethyl butyrate 50 allylcyclohexyl Propanoate 50 10% * α-Damacone 150 Allyl heptanoate 300 Phenoxyethyl isobutyrate 1500 4-t-butyl-cyclohexyl acetate ¹⁾ 500 Hedione (registered trademark) ²⁾ 200 Jasmolactone ³⁾ 40 hexyl salicylate 1000 Berouton ^{(Veloutone) 4) 50 2-} t- butyl-1-cyclohexyl acetate 2500 alpha-ionone (ionone) 0.99 2,4-dimethyl-3-Sik Hexen-1-carbaldehyde ⁵⁾ 150 Total 7000 * in dipropylene glycol 1) Source: Geneva, Switzerland standing Firmenisch SA 2) methyl dihydrojasmonate; origin: Geneva, Switzerland standing Firme
nisch SA 3) (E) -8-decene-5-olide; Source: Firm, Geneva, Switzerland
enisch SA 4) 2,5,5-trimethyl-5-pentyl-1-cyclopentanone; source:
5) Source: Firmenisch SA, Geneva, Switzerland 5) Source: Firmenisch SA, Geneva, Switzerland This base formulation of the apple type has 2000 parts by weight of 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl] methylpropanoate. added. This resulted in a new formulation in which the fruity aspect was clearly stronger with respect to the base formulation. Furthermore, the formulations containing the compounds according to the invention have a very natural, evaluated velvet associative scent of the musk, and the compounds have a much greater aroma of the base formulation. I also gave the volume. In addition, perfumers have found that the diffusion of the formulation is excellent for both its top note and heart note, especially the tenaciousness of this musk compound.
bottom note for ess) and heavy characters
) Was found to be wonderful.

The above odor effect was particularly remarkable and rich when the configuration (1S, 1′R) isomer was used.

The compound of the present invention is represented by the formula (1S, 1′R) -2- [1- (3 ′, 3′-dimethyl-1)
'-Cyclohexyl) ethoxy] -2-methylpropylpropanoate (EP4
(Described in US Pat. No. 72966), a different effect is observed and the resulting formulation has reduced weight and smoothness, and thus has a fruity-appliance.
le) showed a lower aspect, showing clarity and low volume bottom note diffusion. This known formulation was generally lighter, less sticky and less musk odor than the formulation containing the compound of the invention (l).
ess musky-heavy).

Example 3 Preparation of a perfumed formulation A perfumed base formulation was prepared from the following ingredients: parts by weight hexyl acetate 50 tetramethylnonyl acetate ¹⁾ 1500 TCD acetate ²⁾ 1500 methyl cinnamate 250 10% * γ- decalactone (Decalacton) 200 γ- dodecalactone (Dodecalacton) 50 50% * β- damascone (damascone) 250 isopentyl rate ^{(Isopentyrate) 3)} 100 Mirokishido (Myroxyde: registered ^trademark) 4) 100 Berouton ^{(Veloutone) 5)} 700 10 % * bowl GEO monoclonal (Bourgeonal: registered ^trademark) 6) 300 10% * lilial (lilial: registered ^{trademark) 7)} 2700 1% * n- octanal 100 Myall (Mayol: registered trademark ⁸⁾ 200 Total 8000 * dipropylene glycol (DIPG) in 1) Source: Geneva, Switzerland standing Firmenich SA 2) (tricyclo [5.2.1.0 ^2.6] deci-4-yl) methyl acetate; origin: Switzerland Firmenich SA, Geneva 3) 1,3-Dimethyl-3-butenylisobutyrate; Source: Firmenich SA, Geneva, Switzerland 4) Isomeric mixture of osimene epoxide; Source: Fir, Geneva, Switzerland
menich SA 5) See Example 2 6) 3- (4-t-butyl-1-phenyl) propanal; Source: Quest
International 7) 3- (4-t-butyl-1-phenyl) -2-methylpropanal; source: Givaudan-Roure 8) 1-hydroxymethyl-4-isopropylcyclohexane; Bernie, Switzerland; source: Geneva, Switzerland Firmenich SA 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl] is added to the base formulation having a fruity peer type odor.
Addition of 2000 parts by weight of methyl propanoate resulted in a new formulation,
This odor was considerably modulated with respect to the notes of the base formulation. This modulation is mainly due to the fruity peer's associative odor.
), this smell is rich and mellow character (ri
It gains ch and full character and a pronounced and elegant volume, reminiscent of the ripe pear aroma. This voluminous impression persists throughout the slow evaporation of the formulation, and the fruity and elegant tone of the formulation (ton
). This aroma effect was particularly pronounced and rich when isomers having the (1S, 1'R) configuration were added to the base formulation.

Example 4 Preparation of a scented formulation for powder detergents A base scented formulation for powder detergents was prepared by mixing the following ingredients: Ingredients parts by weight citroneria acetate 200 amylcinnamic aldehyde 1000 hexyl Cinnamic aldehyde 2000 10% * Ambrox (registered trademark) DL ¹⁾ 100 isononyl acetate 200 Verdyl acetate 400 Verdyl propionate 500 10% * Intrelevenaldehyde
e) ²⁾ 100 10% * aldehyde 13-13 ³⁾ 200 Coumarin 100 Lirial (registered trademark) ⁴⁾ 1000 4-t-butyl-cyclohexyl acetate ⁵⁾ 1300 Fluramone (registered trademark) ⁶⁾ 200 3-methyl-5-phenyl-1-pentanol ⁷⁾ 500 Hexyl salicylate 700 Tetrahydromuguol ⁸⁾ 400 10% * α-damascon 250 Polywood (registered trademark) 150 Ilaria (registered trademark) ¹⁰⁾ total 300 belt fix-scale (Vertofix coeur) ¹¹⁾ 400 total 10000 * DIPG in 1) racemic tetramethyl perhydro naphthaldehyde furan; origin: Geneva, Switzerland standing Firme ich SA 2) isomer mixture of undecenal; origin: USA resident Internation
al Flavors & Fragrances 3) Tridecanal and 11-methyldodecanal; Source: Firmenich SA, Geneva, Switzerland 4) See Example 3 5) See Example 2 6) 2-heptyl-1-cyclopentanone; Source: International in USA
ionic Flavors & Fragrances 7) Source: Firmenich SA, Geneva, Switzerland 8) Mixture of isomers; Source: International Flavo, USA
rs & Fragrances 9) Perhydro-5,5,8a-trimethyl-2-naphthyl acetate; Source: Firmenich SA, Geneva, Switzerland 10) Mixture of iso-methylionone; Source: Firm, Geneva, Switzerland
enich SA 11) Source: International Flavors & Fra, USA
grands powder-based detergent formulation with 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl] methylpropanoate 1000
Addition of parts by weight resulted in a new formulation, of which the olfactory notes acquired a very pronounced volume and tenaciousness. The typical odor impression imparted by the aldehyde in the base formulation was well maintained by the musk-heavy note of the compound of the present invention. Perfumers have also found that the formulation becomes more diffuse, accentuating the fruity and rose-like tonality of the formulation.

The above-mentioned scent effect can be perceived both from the novel formulation and from the linen washed with a powder detergent scented with said formulation. The musk odor of the aromatic notes of the formulations according to the invention, which would also be able to odor on linens thus treated, is typically provided by polycyclic musk odorous compounds of the indane type It resembled the note, a fascinating, warm, powdery, slightly faint associative notation of animal odor. The best olfactory effect was obtained with the advantageous compounds of the invention, namely the (1S, 1'R) -isomer of the above compounds. The musk effect observed by perfumers was very olfactory closely similar to the musk effect typically provided by Galaxolide® under similar application conditions.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) A61K 7/50 A61K 7/50 A61L 9/01 A61L 9/01 Q C07C 67/08 C07C 67/08 67 / 14 67/14 67/313 67/313 69/36 69/36 69/533 69/533 69/54 69/54 Z 69/716 69/716 Z C11B 9/00 C11B 9/00 TZ C11D 3/50 C11D 3/50 9/44 9/44 // C07B 53/00 C07B 53/00 G C07M 7:00 C07M 7:00 F term (reference) 4C080 AA04 BB02 BB03 CC01 HH03 JJ01 KK03 LL02 MM12 4C083 AC072 AC212 AC341 AC342 AC351 AC352 AC842 CC03 CC17 CC25 CC38 CC50 EE50 4H003 DA02 FA26 4H006 AA01 AB14 AC48 BN10 BR10 KA06 KA14 4H059 BA35 BA67 BB13 BB45 DA09

Claims (11)

[Claims] 1. A compound of formula (I): [Wherein the symbols R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom or a methyl group or an ethyl group, and the symbol X represents an oxygen atom or a formula: Wherein n is an integer of 1 to 3, and symbols R ⁶ and R ⁷ each represent a hydrogen atom or a methyl group or an ethyl group, and R ⁵ represents a C ₁ -C ₄ line. A branched or branched alkyl or alkoxy group, a C ₂ -C ₄ linear or branched alkenyl group or a formula: — (O) C—Y—R ⁸ (wherein Y represents the same as X, R ⁸ represents a C ₁ -C ₄ linear or branched alkyl group or a C ₂ -C ₄ linear or branched alkenyl group). 2. Formula (III): Wherein X is an oxygen atom or an unsubstituted methylene group or an ethylene group, and R ⁵ is a group having 1 to 3 carbon atoms as defined in claim 1. Compound. 3. 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl] methylpropanoate, 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl] methylbutanoate, -(3,3-dimethyl-
1-cyclohexyl) ethyl 4-oxohexanoate, 1- (3,3-dimethyl-1-cyclohexyl) ethyl 5-oxohexanoate, 1-[(3,3-
Dimethyl-1-cyclohexyl) ethoxycarbonyl] methylmethyloxalate, 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl] methyl 2-propenoate and 1-[(3,3-dimethyl-1-cyclohexyl)
[Ethoxycarbonyl] methyl 2-butenoate. 4. 1-[(3,3-Dimethyl-1-cyclohexyl) ethoxycarbonyl] methylpropanoate. 5. A compound according to claim 1, in the form of a stereoisomer of the configuration (1S, 1′R) or a mixture containing a major amount of said isomer and at least one other stereoisomer. A compound according to claim 1. 6. A perfume formulation or perfume product containing the compound according to any one of claims 1 to 5 as a perfume component. 7. A form of perfume or colon, soap, bath or shower gel, shampoo or other hair care product, cosmetic preparation, deodorant or antiperspirant, air freshener, detergent or fabric softener, or universal cleaner. The scented product according to claim 6. 8. The scented composition or scented product according to claim 1, wherein
A method for producing a perfumed compound or perfumed product, characterized by adding the compound described in the above item. 9. In preparing a compound according to any one of claims 1 to 5, a compound of formula IV: An alcohol represented by the formula (V): And esterified with an appropriate derivative thereof and represented by the above-mentioned symbol R ¹
To R ⁵ and X is characterized by representative ones described in claim 1, claims 1-5
A method for producing the compound according to any one of the above. 10. In preparing a compound according to any one of claims 1 to 5, a compound of formula VI: With an alcohol of formula (VII): Esterified and in an acid or the latter suitable derivatives represented the above formula the symbols R ¹ to R ⁵ is characterized by representative ones described in claim 1, any one of claims 1 to 5 A method for producing a compound of the formula: 11. A compound of formula (VI ′): [The symbols R ^{1 to} R ⁴ in the formula are as defined in claim 1].